Synthetic composition comprising hydrolyzed, acetalized, and/or ketalized copolymers of vinyl esters and unsaturated ketones containing at least one ch=c grouping



Patented Oct. 26, 1943 UNITED STATE s PATENT} OF'FlCE SYNTHETIC l COMPOSITION COMPRISING v HYDBOLYZED, ACETALIZED, AND/OR'KE- TALIZED COPOLYMERS OF VINYL ESTERS AND 'UNSATURATED KETONES CONTAIN- V AT LEASE ONE CH2=C GROUPING- Gaetano F. DAlelio, Pittsfleld, Mass., asslgnor to General Electric .Company, a corporation of New York 7 Applicationtlune 7, 1940, Serial No; 339,303

6 Claims. (ci. 114-125) This invention relates to the production of new materials having valuable and characteristic properties that make them especially suitable for use in industry, for example in molding, laminating, coating and'adhesive applications, and for other purposes. The invention; is concerned more particularly with the production of compositions of matter comprising an acetalized,

ketalized -or acetalized and ketalized c opolymer c (or copolymers) of a plurality-of copolymeriz'able materials, one of which is a vinyl ester having at least one grouping and another of which isva ketone containing at least one grouping and no other polymerizable grouping, and reacting the 'partially'hydrolyzed product withan aldehyde or a ketone to introduce acetal or ketal groups into the product. In such acetalized or ketalized products only the acid portion of one of the esters is removed in part. As a result. such treated copolymers are potentially hydrolyzable. Hydrolysis of the acetalized or ketalized interpolymer during service use'of the material would be harmful in many cases, for example where the product is in contact with metals, as the acid liberated by the hydrolysis would pit and corrode the metal surfaces. This dangerof acid formation is even greater if an acrylic ester constitutes a component of the copolymer reactant.

Taking vinyl oleate and vinyl acetate as illustrative'of the compounds previously suggested as suitable for forming a copolymer that subsequently might be acetalized, the following structural formulas illustrate the various steps inthe production of the acetal derivative:

Copolymer reactant before hydrolysis Vinyl acetate Vinyl oleate I OCOCH: OCO(C11H1:) v-c fly-"C n-cn,cucn,- (in-cu,- H-

' CO(C)7H!L&) 000cm vinyl oleate vinyl acetate 1 After hydrolysis of the acetate groups 0H (CHrCH-CHr-( JH-C ITCHCHICH- 000031711) n ocogcnun) 1 After formalization CH|CHTCHr-CHCHr-GHCHzCH- 1 O-CHz-O 0003111119) coowfinio a: The oleic acid 'groups remaining in the molecule are potentially hydrolyzable, as a result of whichthe acetalized products have the disadvantages mentioned above. mer reactants made from vinyl acetate and an acrylic ester, e. g., methyl acrylate, the vinyl ester portion of the copolymer cannot be hydro- I lyzed without at least some hydrolysisof the acrylic ester portion of the copolymer. When such hydrolyzed copolymers are acetalized, ketalized or acetalized and ketalized free acid groups are present in the reaction product as made, since the acrylicacid part of the hydrolyzed c0- polymer cannot be acetalized, ketalized or acetalize d and ketalized. The following'structural formulas illustrate the steps in the formation of an acetalized derivative of a copolymer of vinyl actetate and methyl acrylate:

Copolymer reactant before hydrolysis (-cur-cn-cm-cHcHcH-cmc11 000cm $00011; OCOCH: oocm);

Methyl acrylate vinyl acetate vinyl acetate methyl acrylate Acrylic acid Vinyl Vinyl A lic alcohol alcohol In the case of copoly-r t known-canbe'nmduced-by n: or ke a inns a Methylvlnyl aisaaeez w t srouning: noother polyme'rizable grouping.

I, have discoveredthat synthetic compositions ccpolyme'r of a nlurality oi" 'conolymerisable terials, one oi" whichv least one ands-in I avinyl/whatnot- I v- W tthecross linkedcopolymersthereby suilloientlythermoplastic that,

By using-such cross-linked conolvmers as-startin; the-propertiesat the product,

are beneficially This is.- due to the-tact thet cross-linked. copolymer imparts tothe finished product the-high lmpectstrenathand other desirable properties which characterlze, the starting copolymer; reactant. It wasquite mid unexpeotcdto find' thatz'suchcross ketalized, particularlyinviewof the" gro lltne (e. 3., vinyl l'i'lrimste vinyl acetate;

etc.) and another of which is a ketone having at lea-stone v j cm=C can! seamen-Snare. We: at t vinyl vacetate Cooolfl er reccmntbcto -cnFcm-dwca -omda-om-cncm to-ace. oboe-m $00K methylhetone thesabove i'ormnla to:

lict it will b seenthat such acetels contain no.

ou ing that, initially is. or i hy lyzable to a fl'ee' acid. 111c; met: or; my in ventlon, therefore. esne eiallyvadanted tor I ebnl euoos reqummaapemmnu mm m;-

electrlc strensthhanclapermanent-non-corrosive action when in contact with metals.

f when a. ester havlhz-et CHfC,

grouping at. one other: polymexizable.

groupingispecitlcally-another grouping is, copolymerised with a ketone having,

esinzle i F ketallmd,

toreact with linked coooly'rperscoifldsbe acetalized; ketalized or tact'that thesematerials areinfusible and substantiellytmwluble in "all theordinary solvents. I have they can be mold,- under and-pressure to a desired shape. 'lluftl-cross-ilinkedoomlvmers oi vinyl'esters and ketones; which have been aoetalized',

thismpcrtmiwhlch may be described as semi- 'thermoplasticityf wast-unexpected andunpredictsinoejltgisinconceivable thatthe-cross-linkin the startlng-copolymerwould be.

use

destroyeddin'ing'the'reaotionvwith a.

mylnvention into eflectl lflydrolylie a. p! I a vinyl: ester rowing at least one 'firoupim, ands material conolyrnerizable there- [with comprising aketone containing at least 'sro nmw L thex; the :hydrolyzed-copolymer =oeontamin selected from the class oomsistihm-ot 'aldehydes, ketones' and mixtures of aldehydes and-hatches untilat-least some or the hydroxyl: groups. of the hydrolyzed copolymer have heeni replaeed the corresponding: acetal, k et ailtzoracetalyand ketal groups. ;For example, I may hydrolyze: the copolymer, to at least per cent, more particularly'from to 100, per cent,

0t; that theoretically possible and acetal-ize;

, H as srounlns i cnolyme'rlzed with a.v G00: taming-a.- I

ketallze or acetalize andqketalizethe hydrolyzed 'cooolymer until. at least 10' per cent oi the hydroxyl' Qroupsot the hydrolyzed copolymer have replacedby, 'acetal, ketal oracetalancl'ketal aromas.v In some casesitor instancewhere-the reslstanceo! the product tonwater is or secondary ccmsidoration'. thehydrolyzeducopolymer may have .onlyza-minor-proportion; (that; is, less than percent) oi." its hydroxyl groups: replaced by metal. ketal or acetaltandyketal-Hgroups. For most. a zgpllcattions; however; ity is usually desirable thatiattleastjll per cent; say to. lflili'per cent,

at: the: l'mdroxyl groups otuthe hydrolyzed comlymeltybe replaced by acetal; ketal' oracetaland obtainedwhen the copolymer is hydrolyzed: to

Boto IOO-per cent of that theoretically. posflsibiejond: the hydrolyzed comiymer is acetallzed. ketslizedsor acetallzed-vand ketallzedxuntll fmm' lotto 10031361 cent or the hydroxylsro'ups of the hydrolyzed. cop'olymer" have been replaced by acetal, ketal OPBCQtGIQB-Dd-kEtG-l-Kflfllfiw a r 7 Although," it is possible tocopolymerize (and scammed and ketallzed' would-have kctalggrouns; Particularly valuable nroductsaare grouping.

thereafter hydrolyze and acetaliae, 'ketaliz or acetallze and ketalize) a vinyl ester and other polymerizable lsetones notcontaining a grouping, for example compounds containing the grouping i no=c'c i l where R is an alkyl or aryl radical, a specific example being methyl crotyl ketone,

CH3CO-CH2C 3H=CH-CH'3 the production of such copolymers requires the use of very strong polymerization catalysts, e. g.,

Mainly for economic reasons I prefer to use not morethan 50 per cent by weisht (of the mixture) of the unsaturated ketone in iorming single vinyl ester with one or more unsaturated ketones, I may copolymerize a plurality of such aluminum chloride, boron trifluoride, etc. Such copolymers are less satisfactory, as starting reactants, and their reaction products with aldehydes, ketones or mixtures of aldehydes and ketones have limited utilityas compared with the corresponding reaction products of hydrolyzed copolymers of a vinyl ester and a ketone containing at least one -In order that those skilled in-the art better may understand how to practice this invention, the following more detailed description is given:

Preparation of copolymer In effecting copolymerization between the vinyl esterand the unsaturated ketone the components are mixed and interpolymerized in the presence or absence of a. polymerization catalyst. Preferably a polymerization catalyst is used. Examples of such catalysts are ozone, ozonides, inorganic super-oxides such as barium peroxide, sodium peroxide, etc., aliphatic acyl peroxides, e. g., acetyl peroxide, lauryl peroxide, stearyl peroxide, etc., peroxides of the aromatic acid series, e. g., benzoyl peroxide, etc., mixed peroxides, e. g.,. acetyl benzoyl peroxide, acetyl stearyl peroxide, etc., various per-compounds such as perborates, persulfates, perchlorates, etc., aluminum salts such as the halides, e. g., aluminum chloride, etc., organic and inorganic acids such as methacrylic, hydrofluoric, etc., metal compounds of the unsaturated acids as, for instance, cobalt and manganese resinates, linoleates, maleates, etc. Benzoyl peroxide is the preferred catalyst. Any suitable amount of catalyst may be used, but in general the catalyst concentration will be within the range of 0.1 to 2.0 per cent by weight of the whole.

When rapidity of interpolymerization between the components is of secondary consideration,

copoiymerization maybe effected merely under the influence of heat, light, or heat and light and in the absence of a polymerization catalyst.

The rate of copolymerization and the properties of the starting copolymer reactant vary with the time, concentration and, if a catalyst is used, also with the catalyst concentratiomas well as upon the particular monomers or partial polymers employed in preparing the copolymer and the proportions thereof. Copolymerization may be effected at from room temperature to C.) to temperatures above 100 C., for example about 130 C., but ordinarily I use temperatures within the range 011-60 to 1-20 C. in causing the mixed components to interpolymeriae.

esters with a single orwith a plurality oi unsaturated ketones. Also, in some cases, other organic materials which are copolymerizable with the vinyl ester (or esters) and the unsaturated ketone (or ketones) may be incorporated into the mixture and the whole copolymerized to form a copolymer reactant of improved utility in the production of an acetalized, ketalized or acetalized and ketalized copolymer of particular properties. Examples of such organic materials which may be used with the vinyl ester and the unsaturated ketone in forming the copolymer' reactant are maleate esters, fumarate esters, acrylonitriles, acrylaldehydes, unsaturated ethers having a functionality of 2 or more, etc.

Illustrative examples-o! vinyl esters, in addition to those previously mentioned, which may be employed in preparing the starting copolymer reactant, are the vinyl esters of saturated and unsaturated, aliphatic and aromatic, monobasic and polybasic acids, more specifically the vinyl esters of the following acids: chloroacetic, propionic, bromopropionic, butyric, isobutyric, valeric, caproic, heptylic, caprylic, nonylic, capric, acrylic, alkacrylic (e. g., methacrylic, ethacrylic, etc.), crotonic, oxalic, maionic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, benzoic, toluic, phenyl acetic, phthalic, terephthalic, benzoyl phthalic, benzophenone-2,4' dicarboxylic, cinnamic, tricarballylic, tartaric, citric, lactic, etc., including the alpha unsaturated alpha beta polycarboxylic acids, 6. g., maleic, monohalomaleic, fumaric, monohalofumaric, citraconic, mesaconic, acetylene dicarboxylic, aconitic, itaconic, etc. Additional examples 01' vinyl esters which may be used in preparing the oopolymer reactant are vinyl hexahydroben'zoate, vinyl propyl succinate, vinyl butyl phthaiate, vinyl diethyl citrate, trivinyl citrate, vinyl phenyl acetate, divinyl o-phenylene diacetate, divinyl phenyl butyrate o-carboxylate, trivinyl trimesate, vinyl-o-toluylate, etc. The structural formulas of these last-named vinyl esters are given in my copendingi application Serial No. 336,981, filed May 24, 1940, and assigned to the same assignee as the present invention.

In some 'cases it is of particular advantage to use vinyl esters containing a copolymers may be obtained, for example, by copolymerizinga vinyl ester containing a single grouping with an unsaturated ketone also containing a single grouping. By controlling the extent of hydrolysis and acetalization, ketalization or acetalization and ketalization of such thermoplastic copolymers, acetalized, ketalized or acetalized and ketalized products varying from soft thermoplastic (heat-softening) to hard, semi-thermoplastic solids may be obtained. By copolymergrouping, in addition to those previously mentioned, and which may be used in preparing the starting copolymer reactant, are: Trichlorphenyl vinyl ketone Vinyl methyl ketone CH2 =CH- (JO-CH3 Vinyl ethyl ketone CH2=CH- C Can't Vinyl propyl ketone I CH=,GH-OQ-C:Hr Vinyl isopr'opyl ketone CH: CH2=CH C O-(|JH-CH: Allyl methyl ketone CHz=CH- on,- c 0- on; Allyl ethyl ketone CH2=CH CHT C CzHs Vinyl chlormethyl ketone one- 0H c 0- CHIC] 2-chlor ally] methyl ketone capo-care 0- on,

A l Methallyl methyl ketone 013: (3- on,- o 0- CE: I

I-Hg Vinyl propenyl ketone oH,=oH-o OCil=CH-CH: Diailyl acetone CH:=OH-CH:CHz-C ocnz-cnron=cm izing a vinyl ester containing a. single or a plurality oi CHFG Phenyl vinyl ketone Ally] aceto phenone Vinyl phenethyl ketone CHFCH-C o-om-cmG copolymer may be caused to take place simuitaneously with the 01' the copolymer.

When the copolymer is hydrolyzed separately from the acetalization, ketalization 01'- acetalization and ketalization reaction, this may be done, for example, by heating the copolymer with water and a suitable catalyst, examples or which are strong alkalies (e. g., sodium and potassium hydroxides, tetra-alkyl ammonium hydroxides, etc.) and acidic bodies (e. g., mineral acids such as hydrochloric, sulfuric, etc., and acidic salts such as aluminum chloride, zinc chloride, etc.) until the desired degree of hypartial or complete hydrolysis drolysis has been effected. I prefer to use an acid catalyst. The hydrolyzed product, with or without first being purified (or partially re-eshas been carried farther than desired), then is acetalized, ketalized or acetalized and ketalized by causing it to react under acid conditions with an aldehyde, a ketone, a. mixture of difl'erent aldehydes, a mixture of difierent ketones, or a mixture of a single aldehyde and a single ketone or a plurality of different aldehydes and different ketones. The reaction is continued until the desired percentage ofhydroxylgroups in the hydrolyzed copolymer have been replaced by acetal, ketal or acetal and ketal groups. The solid reaction product then is isolated from the reaction mass, washed and dried.

Preferably I conduct the reaction with the C=O-containing compound, under acid conditions, simultaneously with the hydrolysis of the copolymer. This may be done, for example, by treating the 1:0- polymer with water, an acidic catalyst (examples of which were given in the preceding para graph) and an organic compound containing or engendering an active carbonyl e. 2., aldehydes, ketones, etc. Prefreaction is carried out in the presro p n erably the once oi. a liquiclmedlum adapted to cause a molecular dispersion 01' the reaction product, e. g.,

., n q J. Lot. c MY, cARBON LOMPUUNDS,

in acetic acid. propionic acid. liquid (or liqueflcomp and then with another simul able) monohydric alcohols, e. g., ethyl alcohol, butyl-alcohol, amyl alcohol, etc., mixtures of liquid alcohols, acids and esters, etc. To shorten the time required to acetalize, ketalize or acetalize and ketalize the copolymer, it is desirable to maintain the reactants at an elevated temperature, say 60 to 100 C. or above, the exact temperature depending more or less upon the boiling point of the mixture. Ordinarily the reaction is carried out under reflux at or approaching the boiling point of the reaction mass.

After the conjoint hydrolysis and reaction with the C=O-containing compound has been carried to the desired stage as determined by analysis or by previous experience, the reaction mass usually is mixed with water to which may be added, if desired, a neutralizing agent (e. EL, sodium and potassium hydroxides and carbonates, ammonium hydroxide, etc.) for the acidic bodies. This causes coagulation of the treated copolymer, which thereafter is washed until free of water-soluble materials and then dried. The resulting products can be shaped by the application of heat, pressure or heat and pressure.

As agents for. treating the copolymer I may use any aldehyde or ketone or any compound engendering an aldehyde or a ketone, that is, a compound which will be converted to an aldehyde or a ketone during the reaction. Examples of such compounds are formaldehyde, paraformaldehyde, paraldehyde, trioxymethylene, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, methacrolein, crotonaldehyde, enzaldehyde, cinmic aldehyde, anisaldehyde, p-m yl acetaldehy e, furfural, acetone, chloroacetone, methylvinyl ketone, divinyl ketone, methyl ethyl ketone, acetophenone, benzophenone, quinone, tetrahydroquinone, benzil, benzoyl acetone, acetyl dibenzoyl methane, benzal acetophenone, mesityl oxide, shogaol, cyclohexanone, vanillin, zingerone, alphy-oxy-tetrahydronaphthalene, paeonol, etc.

The properties, for example hardness, of the acetalized, ketalized or acetalized and ketalized copolymer are considerably influenced by the particular treating agent used. Thus, for the same copolymer and the same degree of hydrolysis and acetalization, formaldehyde will yield a harder acetalized copolymer than propionaldehyde. 0n

the other hand, acrolein and furfural yield more O=O-containing compound afterwards, or hydrolysis and condensation with the mixed treating agents may be carried out simultaneously. Or, the hydrolyzed copolymer may be reacted first with one C=0 containing xy pin taneous hydrolysis and partial reaction with one C=0-containing compound agent may be caused to take place, followed by more complete reaction with a different C=O-containing These differences are reflected in the reaction.

products of the copolymer with a C=O-containing organic compound.

By varying the time and temperature of reaction and the concentration of the catalytic agent and of the C=O-containing compound, it is possible to vary the extent of hydrolysis and of the reaction of the copolymer with the O=0-containing compound. If the hydrolysis is carried out in the absence of a 0:0 containing compound, the extent of hydrolysis also may be C 0 containing compound and the ratio of hydroxyl groups to acetal ketal or acetal and ketal groups and the ratio of each to the number of ester groups re-- maining in the molecule. For example, two products with entirely diiferent properties will result from the same copolymer reactant if, in one case, the hydrolysis is carried to per cent of that theoretically possible and then 45 per cent of the available hydroxyl groups are acetalized, ketallzed or acetalized and ketalized while in the other case the hydrolysis is carried to 45 per cent or that theoretically possible and then 90 per cent of the available hydroxyl groups are acetalized, ketalized or acetalized and ketalized. This will be more clearly understood from a consideration of Fig. 1 of the accompanying drawing showing a triangular coordinate graph and from the following discussion of the same.

' compound.

has not been caused to react with a O=O-containing compound; the point E designates a 100 per cent hydrolyzed copolymer: and the point A, a 100 per cent acetalized, ketallzed or acetalized and ketalized copolymer. The area I, designated by the triangle ABC, covers compositions of particular utility in the production of molding compositions and electrically insulating materials. Those compositions within this area that contain less than 20 per cent of hydroxyl groups, of the maximum theoretically possible on complete hydrolysis, are particularly useful in the production of wire enamels. The area II, designated by the triangle CDF, covers compositions having properties more closely approaching those of the starting copolymer reactant than those compositions covered by areas I, III and IV. The area III, designated by the triangle BED, covers compositions of lesser resistance to water than the compositions of the other areas.

- This is because of their higher hydroxyl content as compared with the other compositions. These compositions are more easily dispersed in water. They are particularly adapted for use in the production of water-dispersible and hydroxylatedsolvent-dispersible adhesives. The area IV, designated by the triangle BCD (middle section of the graph), covers compositions having properties intermediate those falling within the other areas. The properties of any particular composition within this area approach those of the compositions falling within the area to which it is nearest.

It will be understood, of course, that the deductions which may be made from this graph are only general and that other variable influences in the production of the treated copolymer may cause some variations. The graph, however, does show the wide variations that are possible in the preparation of the new synthetic compositions of this invention and, in a general way, how the properties of the final product may be varied by varying the extent of the hydrolysis and the extent of the reaction with the C=-00 mining n The properties of these new artificial masses may be varied in still other ways. For example, their properties may be varied by carrying out the reaction with the C=O-conta mg I compound in the presence of other reactants such, for instance, as one or more organic compounds capable of forming a methylol derivative as an intermediate during the resin formation or one or more other compounds capable of reacting with the C=0-containing compound or with the reaction product of the C=0 ntaining compound and the hydrolyzed copolymer. Ex-

amples of such modifying reactants which may be used as such, or in the form of their methylol or methylene derivatives, are phenols, including halogenated (e. g., chlorinated, brominated, etc.) and non-halogenated monohydric and polyhydric phenols, e. g., phenol itself and its homologues such as ortho, meta and para cresols, the xylenols, the butyl, amyl and hexyl phenols, tertiary amyl phenol, cyclohexyl phenol, phenyl phenol, styryl phenol, indene phenol, coumar phenol, resorcinol, chlorophenol, chlorophenyl phenol, chlorostyryl phenol, etc.; hydroxy aromatic esters, e. g., hydroxy benzoates, hydroxy phenyl acetates, hydroxyl phenyl propionates, hydroxy cinnamates, etc.; hydroxy aromatic ethers, e. g., hydroquinone mono-ethers, guaiacols, etc.; monohydric and polyhydric alcohols, e. g., ethyl, propyl, isopropyl, butyl, amyl, etc., alcohols, ethylene glycol, diethylene glycol, glycerine, pentaerythritol, trimethylol nitro methane, etc.; amides, both monoamides' and polyamidea'e. g., formamides, acetamide, stearamide, malonic diamide, succinic diamide, adipic diamide, phthalic diamide, citric triamide, itaconic diamide, sulfonamides such as toluene sulfonamide, benzamide, urea and its homologues and derivatives and substances of the nature of urea, e. g., thiourea, methyl urea, tertiary amyl urea, phenyl thiourea, guanidine, biguanide, guanyl urea, triazines, pseudothiourea, melamine, etc.; amines, e. g., ethylene diamine, aniline, phenylene diamine, amino phenols, etc. v

The following specific examples are givenin order to illustrate more clearly how the present invention may be carried. into effect. All parts are by weight.

Example 1 Seventeen parts of a copolymer made by interpolymerizing parts vinyl acetate and 10 parts methyl isopropenyl ketone were reacted for 48 hours at 60 C. and for an additional 48 hours at 70 C. with Parts Aqueous formaldehyde (approximately 37.1% HCHQ) 10 Concentrated hydrochloric acid 1 1 Acetic acid- Parts Acetone 8 Water 4 Concentrated hydrochloric 'acid 1 Acetic acid- 100 yielding a viscous solution with some evidence of gel structure. After precipitation, washing and drying a hard, brittle resin was obtained. This resin became slightly rubbery when heated at C.

Example 3 Seventeen parts of a copolymer made by interpolymerizing 90 parts vinyl acetate and 10 parts methyl isopropenyl ketone were reacted for various modifying bodies of the hydrolyzed copolymer with the cresyl phosphate,

. salicylates, phthalates, etc.; alkanol amines, e. g., esters corresponding to the structural formulas 48'hours at 60 C. and for an additional 48-hours at 70, c. with yielding an amber-colored gel. The washed and dried material was a solid, tough resin which softened on heating.

Example 4 Seventeen parts of a copolymer made by interpolymerizing 90 parts vinyl acetate and parts methyl isopronpenyl ketone werereacted for 48 hoursat 60 C. and for an additional 48 hours at 70 C. with Parts Aqueous formaldehyde (approximately 37.1% HCHO) Ethyl p-hydroxy benzoate 1'7 Concentrated hydrochloric acid 1 Acetic acid"; 100

yielding ablack solution. Upon precipitation,

washing and drying, a soft, rubbery resin which The fundamental synthetic compositions of this invention may be varied widely by introducing during or after reaction C=0-containlng compound. 'These modifying bodies may take the form of high molecular weight bodies, with or without resinous characteristics, for example, hydrolyzed wood productsplignin, proteins, proteinaldehyde condensation products, furfural condensation products, modified or unmodified, saturated or unsaturated polybasic acid-polyhydric alcohol condensation products, sulfonamide-aldehyde resof this invention. Examples of such modifying.

agents are the phthalate esters, for instance dimethyl phthalate, diethyl phthalate, dibutyl phthalate, etc.; the phosphate esters, e. g., tritriphenyl phosphate, etc.; glycol di-esters, e. g., glycol di-hexoate, glycol acetate hexoate, glycol acetate benzoate, glycol diacetoacetate, etc.; esters of furfuryl and tetrahydrofurfuryl alcohols, e. g., furfuryl and tetrahydrofurfuryl maleates, itaconates, fumarates.

and

mcazcmocoma in which formulas R represents hydrogen, alkyl products of such amines, e. g.,

.ee -atesand the amide esters of e. g; semi-amides corresponding to the structural formulas CONE! GONE: 139 and. o

"COOR' COOR' in which iormulas n represents 1 or more, R represents hydrogen, alkyl or aryl radicals and 1 R represents alkyl or aryl radicals; imides, e. g.,

succinlmideyphthalimide, etc.; and similar substances.

The acetalized or ketalized or acetalized and ketalizedinterpolymers of this invention may be stabilized against discoloration and made more resistant to decomposition under heat, particularly in the presence of air, by incorporating into the reaction mass or into the intermediate or finished products various inhibiting or stabilizing agents. Examples of such agents which may 10 8 be used arephenolic bodies, e. g., phenol, resorcinol, catechol, hydroquinone, .pyrogallol, phloroglucinol, alphaand beta-naphthol, cresols, xylenols, carvacrol, thymol, para-tertiary butyl phenol, para-tertiary amyl phenol, para-phenyl phen'ol; etc.; amines, e.- g., ethyl, propyl, butyl and amyl amines and higher members of the homologous-series, methyl amyl, ethyl hexyl, iso-propylbutyl amines, etc., alkanol amines, e. g., 'mono-, di- -and tri-ethanol amines, etc.,polyamines, e. g., ethylene diamine, triand tetramethylene diamines, etc., aromatic primary, sec- 'ondary and tertiary-amines, e. g., phenyl, naph- -thyl, naphthyl phenyl amines and substitution J benzyl amine, ethyl naphthyl amine, diphenyl methyl amine, etc.; amides, e. g.,aeetamide, benzamide, toluene sulfonamide, succinic diamide, etc.; reaction prod- "ucts of phenols,-of amines and of amides, e.-g., phenol-aldehyde condensation products, aminealdehyde condensation products, amide-aldehyde '-condensation products; and similar substances. The chosen stabilizer (inhibitor) depends largely upon the particular acetalized, ,ketalized or aceti5= alized and ketalized interpolymer to be stabilized andtheparticular service application of the finished -;product. Any suitable amount of stabilizer may be used, but ordinarily only a relatively small proportion, for example from about 0.1 to 3.0 per fill-bent by weight of the treated interpolymer, is

:employed.

Dyes, pigments and opacifiers (e. g., barium sulfate, zinc sulfide, titanium compounds such as theoxides, flaked aluminum, copper and the like) -may be incorporated into the compositions to alter the visual appearance and the optical ."pzoperties of the finished product. Mold lubricants such as the metallic soaps of the high mo- -lecular weight fatty acids, for example the stempalmitates of tin, zinc, etc., waxes such as carnauba, high melting point parafiin waxes, etc., may be added to facilitate molding of the "compositions. Various fillers may be used to -provide a wide variety of molding compositions.

The particular filler depends upon the particular application for which the molded article is to be used. As fillers may be employed, for instance,

. bleached or unbleached wood flour, alpha cellulose in flock form, sheets or cuttings of paper cloth,-canvas, etc., asbestos in powdered or long "or short fiber length including defibrated asbestos, powdered'or -flaked mica, wood chips, short or ions -=wood ilbers, synthetic Ornatural continuwas threaded fibers, glass fibers incontinuous fllaor aryl radicals; the semi-amides of polyestersnu aflflt or fabric (wovenordelted) ioz mgete. mine filled or unfilled synthetic compositions may be densified by working in a Banbury mixer, or by rolling, pelleting or other means, followed by grinding and screening to the desired particle size; The molding compositions may be molded, extruded or injected at elevated temperatures,

e. g., 125 to 225. C., and at suitable pressures,

e. g.. at about 1000 to 20,000 pounds per square inch, usually between about 2000 and 4000 pounds per square inch in compression molding.

In addition to their use in molding compositions and in the production of molded articles,

Such liquid compositions also may containoils,

e. g., linseed oil, China-wood oil, perilla oil, soya bean oil, etc., pigments, plasticizers, driers and other addition agents commonly used in the production of paints. varnishes, lacquers. enamels, etc. Coating compositions made from these new synthetic materials (particularly those which are highly acetalized, ketalized' or acetalized and ketalized, when applied to a base member, e. g., metals, and air-dried or baked, are strong, tough, abrasion-resistant, have good adhesive properties and excellent resistance to heat, water and organic solvents.

Asillustrative of how the synthetic compositions of this invention may be used in the field of electrical insulation the following examples are cited:

A liquid coating composition comprising an acetalized, a ketalized or an acetalized and ketalized interpolymer of the kind above described and a suitable volatile solvent is applied to a metallic conductor such as plain or tinned copper wire, for example by passing the wire through a bath of the coating composition. Thereafter the coated wire is passed through a suitably heated oven to vaporize the solvent and to convert the coating to a hard, tough, flexible, abrasion-, moistureand solvent-resistant state. In some cases it may be desirable to wrap the conductor with a fibrous material, e. g., asbestos in deflbrated or other form or with glass fibers, cotton cloth, paper, etc., before treating it with the solution. A further procedure is to coat and at least partly impregnate the wrapped conductor with a syrupy solution of the treated interpolymer, wind the thusinsulated conductor into the desired coil, and then heat the wound coil to evaporate the solvent and to harden the residual product.

Sheet insulation may be prepared by treating woven or felted organic or inorganic fabrics or paper with these new synthetic materials. Sheet insulation also maybe prepared by binding together flaky inorganic substances with the acetalized, ketalized or acetalized and ketalized interpolymers of this invention. For example, mica fiakes may be cemented and bonded together with an acetalized, a ketalized or an acetalized and ketalized interpolymer to form laminated mica products.

In addition to their use as electrically insulating materials the products of this invention have a wide variety of other applications. For instance, they may be used in the production of so-called safety glass, wherein superimposed layers of glass are firmly united with a binder aasascv plications are organic plastic materials produced by reaction of butyraldehyde with a hydrolyzed copolymer of vinyl acetate and an unsaturated ketone, e. g. divinyl ketone. In such plastic materials the hydroxy groups of the hydrolyzed copolymer are replaced by butyral groups.

The. modified or unmodified products of this invention have a wide variety of other uses, for instance in making interior finishing and construction materials for homes, ofiices, etc., particularly where high-impact-strength and shock-resistant structures are desired. They also may be molded or otherwise suitably shaped to produce buttons, clock cases, radio cabinets, household utensils, decorative novelties, etc. Certain of the synthetic materials of this invention are fiber-forming, that it, they can 'be drawn into continuous filaments. Such filaments may be made into felted or woven fabrics. The highlyacetalized, ketalized or acetalized and ketalized interpolymers are especially adapted for use as water repellents and sizings when applied to wood or the like, orto fibrous materials such as silk, cotton, wool, synthetic organic fibers, etc., in continuous filament. fabric or other form. The synthetic materials of this invention also may be used in making laminated fibrous sheet materials wherein superimposed layers of cloth, paper, etc., are firmly bonded together with the synthetic material; as impregnants for electrical coils and other electrical devices as insulation for motors, generators and other dynamo-electric machines, e. g., as insulation for the coil windings, as slot insulation, in the form of sleevings over electrical connections. as separators between running and starting coil windings, etc.

Fig. 2 of the drawing is across sectional view of an electrical conductor provided with insulation comprising synthetic compositions. of the character described and claimedherein.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. A composition comprising the product of reaction of a taining at least one O 0 -contalning organic compound selected from the class con- .sisting of aldehydes, ketones and mixtures of aldehydes and ketones with a hydrolyzed copolymer of a vinyl ester containing a plurality groupings and a ketone containing at least one cH,=c

grouping.

2. An insulated electrical conductor compris CH1=C/ groupings and another of hich is ketone con product of ingredients of the above numbered column, line -11, for "ketalyzing' read --keta1izing-;

t") page 6, second column, line P ge 7, first. column, line 17,

" assaaor grouping, and (2) a C==O taining -oon v organic compound selected from the class consisting of aldehydes, ketones and mixtures of aldehydes and ketones.

3. The process of preparing new synthetic compositions which comprises reacting with a C= O-contoining compound selected irom the class consisting of aldehydes, ketones and mixtures of aldehydes and keton'es, a hydrolyzed infuslble, insoluble copolymer of a'plurality oi copolymerizable materials, one or which is a vinyl ester having a plurality of CERTIFICATE OF CORRECTION.

Patent No. 2,35 ,897

9 groupings and a ketone containing at least one CHFC/ grouping, and acetilizing the hydrolyzed copolymer until '75 to 100 per cent oi the hydroxyl groups of the hydrolyzed copolymer have been replaced by acetal groups.

5. The process of preparing new synthetic compositions which comprises hydrolyzing an iniusible, insoluble copolymer of a vinyl ester having a plurality of CHFC/ groupings and a ketone containing at least one CHFG/ grouping and ketalizing the hydrolyzed copolymer until 75 to 100 per cent or the hydroxyl groups of the hydrolyzed copolymer have been replaced by ketal groups.

6. A composition comprising the acetal obtained by reaction of formaldehyde with a hydrolyzed iniusible, insoluble copolymer of a viny ester containing a plurality of CH|==C/ groupings and a ketone containing at least one O Y on c v grouping.

GAETANO F. DALELIO.

October 26, 19745. 7

cAE'mno F. D1ALELIO It is hereby certified that error appears in the printed specification column, 22, for .forma'mides' for 'isopronpenyl' read --formamide-- line 6,"strike -out the word "agen read --isopropeny1-- pa for that it read -that 1s--; and that the said Letters patent requiring correction as follows: Page 2, first page 5, second go 8 second column, line 19, Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and seal-edthis (seal) 11th day of January,

Henry Van Arsdale Acting Commissioner of Patents.

- of the above numbered column, line -11, for "ketalyzing' read --keta1izing-;

t") page 6, second column, line P ge 7, first. column, line 17,

" assaaor grouping, and (2) a C==O taining -oon v organic compound selected from the class consisting of aldehydes, ketones and mixtures of aldehydes and ketones.

3. The process of preparing new synthetic compositions which comprises reacting with a C= O-contoining compound selected irom the class consisting of aldehydes, ketones and mixtures of aldehydes and keton'es, a hydrolyzed infuslble, insoluble copolymer of a'plurality oi copolymerizable materials, one or which is a vinyl ester having a plurality of CERTIFICATE OF CORRECTION.

Patent No. 2,35 ,897

9 groupings and a ketone containing at least one CHFC/ grouping, and acetilizing the hydrolyzed copolymer until '75 to 100 per cent oi the hydroxyl groups of the hydrolyzed copolymer have been replaced by acetal groups.

5. The process of preparing new synthetic compositions which comprises hydrolyzing an iniusible, insoluble copolymer of a vinyl ester having a plurality of CHFC/ groupings and a ketone containing at least one CHFG/ grouping and ketalizing the hydrolyzed copolymer until 75 to 100 per cent or the hydroxyl groups of the hydrolyzed copolymer have been replaced by ketal groups.

6. A composition comprising the acetal obtained by reaction of formaldehyde with a hydrolyzed iniusible, insoluble copolymer of a viny ester containing a plurality of CH|==C/ groupings and a ketone containing at least one O Y on c v grouping.

GAETANO F. DALELIO.

October 26, 19745. 7

cAE'mno F. D1ALELIO It is hereby certified that error appears in the printed specification column, 22, for .forma'mides' for 'isopronpenyl' read --formamide-- line 6,"strike -out the word "agen read --isopropeny1-- pa for that it read -that 1s--; and that the said Letters patent requiring correction as follows: Page 2, first page 5, second go 8 second column, line 19, Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and seal-edthis (seal) 11th day of January,

Henry Van Arsdale Acting Commissioner of Patents. 

